Polymerization products and process of preparing them



Patented Aug. 2, 1938 PATENT OFFICE POLYIMERIZATION PRODUCTS AND PROC- ESS OF PREPARING THEM Otto Nicodemus, Heinrich Lange, and Otto Horn,

Frankfort-on-the-Main-Hochst, Germany, assignors to I. G. Farbenindustrie Alrtlengesellschaft, Frankfort-on-the-Main. Germany No Drawing. Application March 9, 1936. Serial No. 67,996. In Germany March 16, 1935 10 Claims.

The present invention 'relates to polymerization porducts and a process of preparing them.

-It is known to transform into polymerization products compounds of the type of the butadiones-1.3, for instance the chlorine derivatives of these bodies, by a suitable treatment with heat or by the application of catalysts. By the polymerization there are obtained either highly polymeric substances of rubberor resinlike properties or there are obtained low polymeric compounds having a more saturated perhaps evena ringshaped constitution, but which at all events cannot further be polymerized as, for instance, the dimerides obtainable from chlor-2- butadiene-L3.

Now we have found that, in contradistinction to the above said, the homologues and substitution products of the butadiene-LZ, that are bodies of the type of allene, may be transformed by a polymerization into new substances of raised molecular weight. s The polymerization may be carried out by the action of light, heat or catalysts with or without an increased pressure in such a manner that each of the named means may be applied alone or in any. combination. According to the operating conditions there may be obtained either low polymeric compounds or.

catechin, amines, copperand others. The reaction may be carried out both continuously and discontinuously with and without an excess pressure. I

The low polymeric compounds obtained according to this method of operating are well defined and in many cases distillable bodies. They show the remarkable property of forming, as

self-drying oils, colorless coatings.

As an excess pressure there may be applied about 1 to 250 atmospheres.

The following examples serve to ilustrate the invention but they are not intended to limit it thereto:

1. Chlor-4-butadiene-L2 is kept boiling for 4s hours on the reflux condenser with exclusion of air. The chlor-4-butadiene-L2 which has not reacted is then distilled and the residue is distilled under a reduced pressure.. At 95 C. to 100 C. and under a pressure of 10 millimeters of mercury a colorless, strongly refractive and 5 terpenellke smelling substance distils which is a dimeric chlormethylallene (CsHmClz). This chlormethylallene may be used either as selfdrying oil or it may be polymerized according to known methods so as to obtain excellent 10 products.

2. Chlor-4-butadiene-L2 is heated for hours with application of pressure to 100 C. A viscous highly polymeric product is obtained which can no longer be distilled. But it may be further ll polymerized in known manner.

3. Chlor-4-butadiene-L2 is passed in a cycle through a reaction vessel which is maintained at C. and is then condensed in a condenser. The condensate is extracted by boiling and re- 20 turned into the cycle. The residue which consists for the most part of dimeric chlormethylallene is worked up as described in Example 1.

4. Thehydroxy-i-butadiene-L2 (boiling point at 68f C. to 70 C. under a pressure of 53- milll- 25 meters) obtained by the action of sodium carbonate in an aqueous solution on chlormethylallene is kept boiling for 48 hours on the reflux condenser with exclusion of air. The hydroxy- 4-butadiene-L2 which has not reacted is dis-' tilled. A viscous highly polymeric product is obtained whichmay be further polymerized in known manner.

5. The methoxy-4-butadiene-L2 (boiling point 40" C. under a pressure of millimeters) ob- 35 tained by the action of methyl iodide on the sodium compound of hydroxymethylallene is kept boiling for 6 hours on the reflux condenser in the presence of a trace of metallic sodium.-

After the distillation of the methoxy-4-butadi- 4 cue-1.2 which has not reacted a viscous highly polymeric product is obtained which may be further polymerized in known manner.

6. The aceto-i-butadiene-Lz (boiling point 85 C. to 86 C. under a pressure of millimeters) 4 obtained by the action ofsodium acetate on chlormethylallene is kept boiling for 3 hours on the reflux condenser in the presence of a small quantity of benzoylperoxide. After the distillation .of the aceto-4-butadiene-L2 which has not 50 reacted a viscous highly polymeric product is obtained which may be further polymerized in known manner. I

7. The cyano-4 -butadiene-1.2 (boiling point 68 C. under a pressure of 80 millimeters) ob- 55 tained by the action o! chlormethylallene on potassium cyanide is heated for 24 hours to about '80" C. under a pressure of 50 atmospheres. After the distillation of the cyano-4-butadiene-L2 which has not reacted a highly viscous polymerization product is obtained which may be further polymerized in known manner.

- 8. The mercapto-Qbutadiene-Lfl (boiling point v50 C..to 52 C. under a pressure of 80 millimeters) obtained by the action of chlormethylallene on sodium sulfhydrate is kept boiling for 5 hours,

in the presence oi. a small quantity of potassium. A solid polymerization product is obtained during this operation.

9. The phenoxy-4-butadiene-L2 (boiling point 90' C. to 95 C. under a pressure of millimeters) obtained by the action of chlormethylallene onsodium phenolate is kept boiling for 48 hours. The phenoxy-4-butadiene-12 which has not reacted is distilled. A resinous polymerization product is obtained during this operation.

10. The n-butylamino-4-butadlene-1.2 (boiling point 54' C. to 55 C. under a pressure oi '7 millimeters) obtained by the action of chlormethylallene on n-butylamine is kept boiling for 48 hours on a reflux condenser with exclusion of air. has not reacted is distilled. A highly viscous polymerization product is obtained which may be further polymerized in known manner.

11. The diethylamino-4-butadiene-12 (boiling point 31 C. to 33 C. under a pressure of 8 millimeters) obtained by the action of chlormethylallene on diethylamine' is exposed for 48 hours to the action of ultra-violet light. After the distillation oi the diethylamino-4-butadiene-L2 which has not reacted a viscous polymerization Weclaim:

1. The process which comprises polymerizing a d-substitution product of butadiene-L2 by The n-butylamino-4-butadiene-1.2 which heating the monomeric material to about its boiling point for at least about 24 hours.

2. The process which comprises polymerizing a 4-substitution product of butadiene-1.2 by heating the monomeric material to about its boiling point for at least about 24 hours while applying pressure.

' 3. The process which comprises polymerizing a- 4-substitution product of butadiene-1.2 by

heating the monomeric material to about its boilat least about 24 hours.

"I. Polymerized 4-substitution products of butadiene-1.2 which are substantially identical with the product obtained by the process defined in claim 1, said products being of oily to resinous character.

8. Polymerized dimeric ch10r-4-butadiene-L2 which is substantially identical with the product obtained by the process defined in claim 4, said product being an oily colorless liquid capable of being further, polymerized.

9. Polymerized methoxy-4-butadiene-1.2, which is substantially identical with the product obtained by the process defined in claim 5, said product being viscous and capable of being further polymerized.

10. Polymerized n-butylamino-i-butadiene-1.2, which is substantially identical with the product obtained by the process defined in claim 6, said product being viscous and capable of being further polymerized.

OI'IO NICODEMU S. HEINRICH LANGE. OTI'O HORN. 

